Azo dyes from aniline having 1 or 2 sulfated hydroxyalkoxycarbonyl or N-(hydroxyalkyl)carbamoyl groups on its ring

ABSTRACT

This invention relates to azo dyes in which the diazotized amino component bears 1 or 2 sulfated hydroxyalkoxycarbonyl or N-(hydroxyalkyl)carbamoyl groups on its ring. These dyes have excellent dyeing and fastness properties on polyamide fibers and also impart color to cellulose acetate fibers and wool. 
     The dyes correspond to the general formula: ##STR1## wherein R 1  represents up to three of a large variety of groups such as alkyl, alkoxy, acyl, arylthio, and the like; X&#39; is O, NH, N(alkyl)- or N(aryl)-; Z is selected from straight- or branched-chain alkylene which may be substituted, for example, with phenyl, halogen, OSO 3  M, alkoxy, aryloxy and the like; M is H, Na, K or NH 4  ; n is 1 or 2; and the coupler C is selected from a variety of couplers including anilines, tetrahydroquinolines, phenols and the like.

This invention concerns novel dyes in which the diazo moieties contain sulfate groups. These dyes are substantially water soluble and are particularly useful for dyeing polyamide, wool and the like, and exhibit excellent properties, including fastness to light and dyeability.

The dyes of this invention correspond to the general formula: ##STR2## wherein the phenyl radical is from diazotized aniline which may be substituted further as defined below; C is the coupler portion of the molecule; X' is O, NH, N(alkyl)-, or N(aryl)-; Z is selected from straight- or branched-chain alkylene, which may be substituted, for example, with phenyl, halogen, OSO₃ M, alkoxy or aryloxy groups, --CH₂ (CH₂)_(m) V--CH₂ (CH₂)_(p) --, where m is 1, 2 or 3, p is 0, 1, 2 or 3, and V is O, S, SO₂, --SO₂ NH--, --SO₂ N(alkyl)-, --SO₂ N(aryl), --N(SO₂ aryl)-, --NH, --NHCO--, --NHCONH, --N(SO₂ alkyl), or --CON(alkyl); M is H, Na, K or NH₄ ; and n is 1 or 2.

More particularly, the dyes correspond to the formula above wherein the aniline ring, in addition to the ##STR3## group or groups, may have 1-3 other substituents represented by R¹ in place of the hydrogens, each R¹ being independently selected from alkyl, alkoxy, thiocyano, alkylthio, arylazo, arylthio, aroyl, carbamoyl, alkylcarbamoyl, acyl, alkylsulfonyl, arylsulfonyl, sulfamoyl, SO₂ NH(alkyl), SO₂ N(dialkyl), alkylsulfonamido, acylamido, halogen, trifluoromethyl and SO₃ (aryl); and the coupler C is selected from ##STR4## wherein

R² and R¹⁴ each represents up to three groups selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R³ in which X is --CO--, --COO--, or --SO₂ -- and

R³ is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R³ also is selected from hydrogen, amino, alkylamino, alkylcarbamoyl, dialkylamino, arylamino, aryl, and furyl;

R⁴ and R⁵ are each selected from hydrogen, alkyl, aryl, cycloalkyl and R⁴ and R⁵ together represent a single, combined group --CH₂ CH₂ CH₂ CH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, --CH₂ CH₂ --S--CH₂ CH₂ --, and --CH₂ CH₂ --SO₂ --CH₂ CH₂ --;

R⁸ is one or two groups each selected from hydrogen, alkyl and alkyl substituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, cyclohexoxy, --OH, --Cl and Br;

R⁹, R¹⁰ and R¹¹ are each selected from hydrogen, alkyl, phenyl, or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkylthio, benzylthio, cyclohexylthio, phenylthio and substituted phenylthio;

Q and Q' are each selected from --CO--, --SO₂ --, or --CN; R¹² and R¹³ are each selected from hydrogen, alkyl, hydroxyalkyl, alkoxy, alkoxycarbonylamino, trifluoromethyl, phenyl or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkoxycarbonylalkyl, cyanolalkyl, amino, haloalkyl, alkylamino, alkylthio, benzylthio, cyclohexylthio, phenylthio and substituted phenylthio; R¹² and R¹³ may combine to form an alkylene bridge of 2 or 3 carbons, or to form an arylene or cycloalkylene radical of 5-6 carbons connecting Q and Q'; R¹⁶ and R¹⁷ are selected from hydrogen, cycloalkyl, aryl, alkyl, and alkyl substituted with alkoxy, hydroxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, sulfamoyl, acylamido, or alkenylsulfonyl, and aryl substituted with hydroxyalkyl; e is 1 or 2; and t and t' are each 1 or zero. It is noted that when t or t' is zero, the corresponding Q or Q' group is --CN;

Each of the aliphatic portions of the above alkyl, cycloaliphatic, alkoxy, alkanoyl and the like groups, as well as the aryl and aryloxy groups, may be substituted further with up to three of the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; ##STR5## wherein Y is --NH--, --NH--alkyl-, --O--, --S--, or --CH₂ O--; --S--R⁶ wherein R⁶ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, triazolyl, or ##STR6## --SO₂ R³ ; --COOR³ ; --OXR³ ; --NH--X--R³ ; --X--R³ ; --OCO--R³ ; --CONR⁷ R⁷ ; --SO₂ NR⁷ R⁷ ; wherein R³ and X are as defined above and each R⁷ is selected from H and R³ ; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy or phenoxy substituted with one or more of alkyl, alkoxy or halogen. All of the aliphatic portions of the various groups herein contain from 1-6 carbons, and are straight or branched chain.

The dyes of this invention impart red to blue shades on fibers, particularly polyamides, and are especially useful for dyeing polyamide (nylon) carpets, giving good fastness to light, ozone, oxides of nitrogen, washing, sublimation, crocking and the like, and having good leveling, transfer, exhaustion, and build properties.

The couplers used in this invention are prepared according to known procedures. The dyes may be prepared by reacting the coupler with a diazonium salt which contains one or two carbalkoxy groups. The product is reacted first with an aminoalcohol H--X'--Z--OH (X' is NH, Z is alkylene) to convert to a N-(hydroxyalkyl)carbamyl group, or with an alkanediol H--X'--Z--OH (X' is O, Z is alkylene) to convert to a hydroxyalkoxycarbonyl group. Subsequently, the material is reacted with concentrated sulfuric acid to form the sulfate ester: ##STR7##

Alternatively, a diazotizable amine containing a hydroxyalkoxycarbonyl group or a N-(hydroxyalkyl)carbamyl group may be sulfated before diazotization and coupling: ##STR8##

This invention will be further illustrated by the following examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention. The compounds listed in the tables below can be prepared by procedures well known to the art. In these tables, the "Position" column refers to the position of the ##STR9## group or groups on the aniline diazo ring.

                                      TABLE 1                                      __________________________________________________________________________      ##STR10##                                                                     Position                                                                            R.sup.1       R.sup.2    R.sup.4  R.sup.5  X'Z         M                  __________________________________________________________________________     2    H             2-CH.sub.3, 5-NHCOCH.sub.3                                                                H        C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          Na                 2    H             H          C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                            4        N(CH.sub.3)C.sub.2                                                             H.sub.4     "                  2    H             3-CH.sub.3 C.sub.2 H.sub.4 Cl                                                                      C.sub.2 H.sub.4 CN                                                                      NHC.sub.2 H.sub.4                                                                          K                  2    H             "          "        "        NHCH.sub.2 CH(C.sub.6                                                          H.sub.5)    K                  2    H             3-CH.sub.3 C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           Na                 2    H             3-NHCOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 CN                                                                      NHC.sub.2 H.sub.4                                                              OC.sub.2 H.sub.4                                                                           Na                 2    H             2-OCH.sub.3, 5-NHCOCH.sub.3                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             NHC.sub.2 H.sub.4                                                                          NH.sub.4           2    4-C.sub.6 H.sub.5NN                                                                          3-Cl       C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.13                                                                        OC.sub.2 H.sub.4                                                                           K                  2    4-Br          2-Cl       H        C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           K                  2    4,6-Br.sub.2  2-CH.sub.3, 3-Cl                                                                          H        CH.sub.2 C.sub.6 H.sub.5                                                                NHC.sub.3 H.sub.6                                                                          K                  2    6-Br          H          C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 CN                                                                      OC.sub.2 H.sub.4                                                                           NH.sub.4           2    4-CH.sub.3 SO.sub.26-Br                                                                      H          C.sub.2 H.sub.4 OSO.sub.3 K                                                             C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          K                  2    H             3-CH.sub.3 C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  2,3  H             3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 CONH.sub.2                                                              "           "                  3,5  H             H          "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     Na                 3,5  2,4-Br.sub.2  "          "        H        NHC.sub.2 H.sub. 4             2    4-SO.sub.2 CH.sub.36-Cl                                                                      H          CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                              NHC.sub.2 H.sub.4                                                                          Na                 2    5-NHCOCH.sub.3                                                                               H          CH.sub.2 CH.sub.2SCH.sub.2 CH.sub.2                                                              NHC.sub.2 H.sub.4                                                                          Na                 2    6-CONHC.sub.6 H.sub.5                                                                        H          CH.sub.2 CH.sub.2SO.sub.2CH.sub.2 CH.sub.2                                                       NHC.sub.2 H.sub.4                                                                          Na                 2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                H          CH.sub.2 CH.sub.2NHCH.sub.2 CH.sub.2                                                             NHC.sub.2 H.sub.4                                                                          Na                 2    4-Cl6-SC.sub.6 H.sub.5                                                                       H          CH.sub.2 CH.sub.2NCOCH.sub.3CH.sub.2                                           CH.sub.2          NHC.sub.2 H.sub.4                                                                          Na                 2    4-C.sub.2 H.sub.5                                                                            3-CH.sub.3 H        C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                       NHC.sub.2 H.sub.4                                                                          Na                 2    4-OCH.sub.3   2-OC.sub.6 H.sub.5                                                                        C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                     "           "                  2    4-SCN         2-SCH.sub.3                                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5  NHC.sub.2 H.sub.4                                                                          K                  2    4-Br 6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                   3-SC.sub.6 H.sub.5                                                                        CONH.sub.2                                                                              C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5  NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                  2    5-NHCOCH.sub.3                                                                               3-NHCOOCH.sub.3                                                                           C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           Na                 3    H             3-NHSO.sub.2 CH.sub.3                                                                     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 CN                                                                      NHC.sub.2 H.sub.4                                                              OC.sub.2 H.sub.4                                                                           Na                 3    2-COCH.sub.3  2-OCH.sub.3, 5-NHCOCH.sub.3                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             NHC.sub.2 H.sub.4                                                                          NH.sub.4           3    2-COCH.sub.3  3-NHCOCH.sub.2 Cl                                                                         C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.13                                                                        OC.sub.2 H.sub.4                                                                           K                  3    2-COCH.sub.34,6-Br.sub.2                                                                     3-NHCOC.sub.2 H.sub.4 OH                                                                  H        C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           K                  4    H             2-CH.sub.3, 3-Cl                                                                          H        CH.sub.2 C.sub.6 H.sub.5                                                                NHC.sub.3 H.sub.6                                                                          K                  4    2,6-Br.sub.2  2-NHCONHC.sub.2 H.sub.5                                                                   C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 CN                                                                      OC.sub.2 H.sub.4                                                                           NH.sub.4           4    2,6-(CONH.sub.2).sub.2                                                                       2-NHCON(C.sub.2 H.sub.5).sub.2                                                            C.sub.2 H.sub.4 OSO.sub.3 K                                                             C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          K                  6    2,3-CON(C.sub.2 H.sub.5)CO                                                                   3-CH.sub.3 C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  2    4,5-NC(CH.sub.3 CONH)S                                                                       3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 CONH.sub.2                                                              "           "                  2    3,4-SNN       H          "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           Na                 2    4-SCN         H          "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  2    4-SO.sub.2 CH.sub.3                                                                          H          "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  4    2-CONH.sub.2  3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  4    2-SC.sub.6 H.sub.5                                                                           3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  2    4-Cl          3-NHCOCH.sub.3                                                                            "        C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                  __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR11##                                                                     Position                                                                            R.sup.1       R.sup.2   R.sup.8 R.sup.4   X'Z         M                   __________________________________________________________________________     2    H             7-CH.sub.3                                                                               2-CH.sub.3                                                                             C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           Na                  2    H             7-CH.sub.3                                                                               2-CH.sub.3                                                                             C.sub.2 H.sub.4 OSO.sub.3 K                                                              NHC.sub.2 H.sub.4                                                                          K                   2    H             H         H       C.sub.2 H.sub.4 OC.sub.6 H.sub.11                                                        OC.sub.2 H.sub.4                                                                           Na                  2    H             5-CH.sub.3                                                                               H       C.sub.4 H.sub.9                                                                          NHC.sub.2 H.sub.4                                                                          Na                  2    H             7-CH.sub.3                                                                               2-CH.sub.3                                                                             C.sub.2 H.sub.4 NHCOCH.sub.3                                                             "           "                   2    H             7-CH.sub.3                                                                               2,2,4-(CH.sub.3).sub.3                                                                 "         N(C.sub.2 H.sub. 5)C.sub.2                                                     H.sub.4     "                   2    H             8-CH.sub.3                                                                               H       C.sub.2 H.sub.4 Cl                                                                       OC.sub.2 H.sub.4                                                                           NH.sub.4            2    4-C.sub.6 H.sub.5NN                                                                          H         2,2,4-(CH.sub.3).sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                                OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                   2    4-Br          7-NHCOCH.sub.3                                                                           "       C.sub.2 H.sub.4 Br                                                                       NHC.sub.2 H.sub.4                                                                          K                   2    4,6-Br.sub.2  "         5-CH.sub.3                                                                             CH.sub.2 CHOHCH.sub.2 OH                                                                 OC.sub.2 H.sub.4                                                                           K                   2    6-Br          7-CH.sub.3                                                                               2-CH.sub.3                                                                             CH.sub.3  NHC.sub.2 H.sub.4                                                                          K                   2    4-CH.sub.3 SO.sub.26-Br                                                                      7-C.sub.6 H.sub.11                                                                       3-OH    C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        NHC.sub.2 H.sub.4                                                                          Na                  2    H             7-OC.sub.6 H.sub.5                                                                       3-CN    C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                      N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     "                   2,3  H             7-SCH.sub.3                                                                              3-OCOCH.sub.3                                                                          C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5   NHC.sub.2 H.sub.4                                                                          K                   3,5  H             7-SC.sub.6 H.sub.5                                                                       2-CH.sub.3                                                                             C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5   NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                   3,5  2,4-Br.sub.2  7-NHCOOCH.sub.3                                                                          "       C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           Na                  2    4-SO.sub.2 CH.sub.36-Cl                                                                      7-NHSO.sub.2 CH.sub.3                                                                    2-C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 CN                                                                       NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     Na                  2    5-NHCOCH.sub.3                                                                               7-OCH.sub.3                                                                              3-OCOCH.sub.3                                                                          C.sub.2 H.sub.4 OCOCH.sub.3                                                              NHC.sub.2 H.sub.4                                                                          NH.sub.4            2    6-CONHC.sub.6 H.sub.5                                                                        7-NHCOCH.sub.2 Cl                                                                        3-OH    C.sub.6 H.sub.13                                                                         OC.sub.2 H.sub.4                                                                           K                   2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                7-NHCOC.sub.2 H.sub.4 OH                                                                 3-CONH.sub.2                                                                           C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           K                   2    4-Cl6-SC.sub.6 H.sub.5                                                                       7-CH.sub.3, 5-Cl                                                                         3-Cl    CH.sub.2 C.sub.6 H.sub.5                                                                 NHC.sub.3 H.sub.6                                                                          K                   2    4-C.sub.2 H.sub.5                                                                            7-NHCONHC.sub.2 H.sub.5                                                                  3-OC.sub.6 H.sub.5                                                                     C.sub.2 H.sub.4 CN                                                                       OC.sub.2 H.sub.4                                                                           NH.sub.4            2    4-OCH.sub.3   7-NHCON(C.sub.2 H.sub.5).sub.2                                                           3-OC.sub.6 H.sub.5                                                                     C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                          K                   2    4-SCN         7-CH.sub.3                                                                               3-SC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.4 NHCOCH.sub.3                                                             "           "                   2    4-Br6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                    7-NHCOCH.sub.3                                                                           3-CONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CONH.sub.2                                                               "           "                   2    5-NHCOCH.sub.3                                                                               H         3-OCH.sub.3                                                                            C.sub.2 H.sub.4 NHCOCH.sub.3                                                             "           Na                  2    4-SCN         7-CH.sub.3                                                                               2,2,4-tri-CH.sub.3                                                                     C.sub.2 H.sub.5                                                                          "           "                   2    4-SO.sub.2 CH.sub.3                                                                          "         "       "         "           "                   4    2-CONH.sub.2  3-NHCOCH.sub.3                                                                           "       "         "           "                   4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "         "       "         "           "                   4    2-SC.sub.6 H.sub.5                                                                           "         "       "         "           "                   2    4-Cl          "         "       "         "           "                   __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR12##                                                                     Position                                                                            R.sup.1       R.sup.2   R.sup.8 R.sup.4   X'Z         M                   __________________________________________________________________________     2    H             6-NHCOCH.sub.3                                                                           3-CH.sub.3                                                                             C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                          Na                  2    H             6-CH.sub.3                                                                               3-CH.sub.3                                                                             C.sub.2 H.sub.5                                                                          OC.sub.2 H.sub.4                                                                           Na                  2    H             6-Cl      "       C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           K                   2    H             6-Br      2,3-di-CH.sub.3                                                                        C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        "           NH.sub.4            2    H             6-F       3-CH.sub.3                                                                             "         NHC.sub.2 H.sub.4                                                                          K                   2    H             H         2-CH.sub.2 OH                                                                          CH(CH.sub.3).sub.2                                                                       "           "                   2    H             H         2-CH.sub.2 OH                                                                          "         N(CH.sub.3)C.sub.2                                                                         ".sub.4             2    4-C.sub.6 H.sub.5NN                                                                          6-NHCOCH.sub.3                                                                           2-CH.sub.2 Cl                                                                          C.sub.2 H.sub.5                                                                          NHC.sub.3 H.sub.6                                                                          Na                  2    4-Br          "         3-CH(CH.sub.3).sub.2                                                                   C.sub.2 H.sub.4 OCH.sub.3                                                                NHC.sub.2 H.sub.4                                                                          Na                  2    4,6-Br.sub.2  6-CH.sub.3                                                                               3-CH.sub.3                                                                             "         "           Na                  2    6-Br          6-C.sub.6 H.sub.11                                                                       2-CH.sub.2 OC.sub.6 H.sub.5                                                            C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        NHC.sub.2 H.sub.4                                                                          Na                  2    4-CH.sub.3 SO.sub.26-Br                                                                      6-OC.sub.6 H.sub.5                                                                       2-CH.sub.2 OC.sub.2 H.sub.5                                                            C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                      "           "                   2    H             6-SCH.sub.3                                                                               ##STR13##                                                                             C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5   NHC.sub.2 H.sub.4                                                                          K                   2,3  H             6-SC.sub.6 H.sub.5                                                                       2-CH.sub.2 Cl                                                                          C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5   NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                   3,5  H             6-NHCOOCH.sub.3                                                                          2-CH.sub.2 OH                                                                          C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           Na                  3,5  2,4-Br.sub.2  6-NHSO.sub. 2 CH.sub.3                                                                   "       C.sub.2 H.sub.4 CN                                                                       NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     Na                  2    4-SO.sub.2 CH.sub.36-Cl                                                                      8-OCH.sub.3, 5-NHCOCH.sub.3                                                               ##STR14##                                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                              NHC.sub.2 H.sub.4                                                                          NH.sub.4            2    5-NHCOCH.sub.3                                                                               6-NHCOCH.sub.2 Cl                                                                        "       C.sub.6 H.sub.13                                                                         OC.sub.2 H.sub.4                                                                           K                   2    6-CONHC.sub.6 H.sub.5                                                                        6-NHCOC.sub.2 H.sub.4 OH                                                                 3-C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OH                                                                       OC.sub.2 H.sub.4                                                                           K                   2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                8-CH.sub.3, 5-Cl                                                                         "       CH.sub.2 C.sub.6 H.sub.5                                                                 NHC.sub.3 H.sub.6                                                                          K                   2    4-Cl6-SC.sub.6 H.sub.5                                                                       6-NHCONHC.sub.2 H.sub.5                                                                  2-CH.sub.2 OC.sub.6 H.sub.5                                                            C.sub.2 H.sub.4 CN                                                                       OC.sub.2 H.sub.4                                                                           NH.sub.4            2    4-C.sub.2 H.sub.5                                                                            6-NHCON(C.sub.2 H.sub.5).sub.2                                                           2-CH.sub.2 OC.sub.6 H.sub.5                                                            C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                          K                   2    4-OCH.sub.3   6-OC.sub.6 H.sub.5                                                                       H       C.sub.2 H.sub.4 NHCOCH.sub.3                                                             "           "                   2    4-SCN         6-NHCOCH.sub.3                                                                           "       C.sub.2 H.sub.4 CONH.sub.                                                                "           "                   2    4-Br6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                    H         "       C.sub.2 H.sub.4 NHCOCH.sub.3                                                             N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     Na                  2    4-SCN         6-CH.sub.3                                                                               3-CH.sub.3                                                                             C.sub.2 H.sub.5                                                                          NHC.sub.2 H.sub.4                                                                          "                   2    4-SO.sub.2 CH.sub.3                                                                          "         "       "         "           "                   4    2-CONH.sub.2  3-NHCOCH.sub.3                                                                           "       "         "           "                   4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "         "       "         "           "                   4    2-SC.sub.6 H.sub.5                                                                           "         "       "         "           "                   2    4-Cl          "         "       "         "           "                   __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR15##                                                                     Position                                                                            R.sup.1       R.sup.9  R.sup.2   R.sup.4  X'Z         M                   __________________________________________________________________________     2    H             C.sub.6 H.sub.5                                                                         H         CH.sub.3 NHC.sub.2 H.sub.4                                                                          Na                  2    H             CH.sub.3 6-CH.sub.3                                                                               CH.sub.3 "           "                   2    H             "        "         C.sub.6 H.sub.5                                                                         "           "                   2    H             "        H         C.sub.2 H.sub.5                                                                         "           "                   2    H             C.sub.6 H.sub.5                                                                         H         H        "           "                   2    H             "        "         CH.sub.3 "           "                   2    H             CH.sub.3 "         CH.sub.3 N(CH.sub.3)C.sub.2                                                                         ".sub.4             2    4-C.sub.6 H.sub.5NN                                                                          "        5-OC.sub.2 H.sub.5                                                                       "        NHC.sub.3 H.sub.6                                                                          "                   2    4-Br          CH.sub.3 "         H        NHC.sub.2 H.sub.4                                                                          "                   2    4,6-Br.sub.2  C.sub.6 H.sub.4p-Br                                                                     H         H        "           "                   2    6-Br          C.sub.6 H.sub.5                                                                         "         C.sub.2 H.sub.4 CONH.sub.2                                                              "           K                   2    4-CH.sub.3 SO.sub.26-Br                                                                      C.sub.6 H.sub.4p-OCH.sub.3                                                              "         C.sub.2 H.sub.4 CN                                                                      N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     K                   2    H             "        5-C.sub.6 H.sub.11                                                                       C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                       NHC.sub.2 H.sub.4                                                                          "                   2,3  H             C.sub.2 H.sub.4 CN                                                                      6-OC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 (COCH.sub.3).sub.2                                                      "           "                   3,5  H             C.sub.2 H.sub.4 OCOCH.sub.3                                                             6-SCH.sub.3                                                                              C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5  NHC.sub.2 H.sub.4                                                                          K                   3,5  2,4-Br.sub.2  CH.sub.3 6-SC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2                                             H.sub.5  NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                   2    4-SO.sub.2 CH.sub.36-Cl                                                                      "        6-NHCOOCH.sub.3                                                                          C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           Na                  2    5-NHCOCH.sub.3                                                                               C.sub.3 H.sub.7                                                                         6-NHSO.sub.2 CH.sub.3                                                                    C.sub.2 H.sub.4 CN                                                                      NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     Na                  2    6-CONHC.sub.6 H.sub.5                                                                        CH.sub.3 6-OCH.sub.3,                                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             NHC.sub.2 H.sub.4                                                                          NH.sub.4                                        5-NHCOCH.sub.3                                     2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.2 Cl                                                                        C.sub.6 H.sub.13                                                                        OC.sub.2 H.sub.4                                                                           K                   2    4-Cl6-SC.sub.6 H.sub.5                                                                       "        6-NHCOC.sub.2 H.sub.4 OH                                                                 C.sub.2 H.sub.4 OH                                                                      OC.sub.2 H.sub.4                                                                           K                   2    4-C.sub.2 H.sub.5                                                                            "        "         CH.sub.2 C.sub.6 H.sub.5                                                                NHC.sub.3 H.sub.6                                                                          K                   2    4-OCH.sub.3   C.sub.2 H.sub.5                                                                         6-NHCONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CN                                                                      OC.sub.2 H.sub.4                                                                           NH.sub.4            2    4-SCN         C.sub.6 H.sub.4p-OCH.sub.3                                                              6-NHCON(C.sub.2 H.sub.5).sub.2                                                           C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          K                   2    4-Br6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                    C.sub.2 H.sub.5                                                                         6-CH.sub.3                                                                               C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           "                   2    5-NHCOCH.sub.3                                                                               C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 CONH.sub.2                                                              "           "                   3    H             CH.sub.3 H         C.sub.2 H.sub.4 NHCOCH.sub.3                                                            "           Na                  3    2-COCH.sub.3  "        "         C.sub.2 H.sub.4 Cl                                                                      "           "                   3    2-COCH.sub.3  C.sub.6 H.sub.4p-CH.sub.3                                                               6-OH      "        "           "                   2    4-SCN         C.sub.6 H.sub.5                                                                         H         H        "           Na                  2    4-SO.sub.2 CH.sub.3                                                                          "        "         "        "           "                   4    2-CONH.sub.2  3-NHCOCH.sub.3                                                                          "         "        "           "                   4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "        "         "        "           "                   4    2-SC.sub.6 H.sub.5                                                                           "        "         "        "           "                   2    4-Cl          "        "         "        "           "                   __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR16##                                                                     Position                                                                            R.sup.1       R.sup.9 R.sup.10 X'Z         M                              __________________________________________________________________________     2    H             C.sub.6 H.sub.5                                                                        H        NHC.sub.2 H.sub.4                                                                          Na                             2    H             CH.sub.3                                                                               "        OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                          Na                             2    H             CH.sub.3                                                                               H        OC.sub.2 H.sub.4                                                                           Na                             2    H             CH.sub.3                                                                               C.sub.6 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          Na                             2    H             CH.sub.3                                                                               C.sub.6 H.sub.5                                                                         NHC.sub.3 H.sub.6                                                                          Na                             2    H             C.sub.6 H.sub.5                                                                        CH.sub.3 NHC.sub.2 H.sub.4                                                                          Na                             2    H             C.sub.6 H.sub.5                                                                        "        "           NH.sub.4                       2    4-C.sub.6 H.sub.5 NN                                                                         "       "        N(C.sub.2 H.sub.5)C.sub.2 H.sub.4                                                          "                              2    4-Br          CH.sub.3                                                                               H        NHC.sub.2 H.sub.4                                                                          K                              2    4,6-Br.sub.2  "       H        NH(CH.sub.2).sub.5                                                                         K                              2    6-Br          C.sub.6 H.sub.4p-Br                                                                    "        OC.sub.2 H.sub.4                                                                           K                              2    4-CH.sub.3 SO.sub.26-Br                                                                      C.sub.6 H.sub.4p-OCH.sub.3                                                             "        OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                          K                              2    H             "       Br       NHC.sub.2 H.sub.4                                                                          K                              2,3  H             C.sub.2 H.sub.4 CN                                                                     Br       N(C.sub.6 H.sub.5)C.sub.2 H.sub.4                                                          K                              3,5  H             C.sub.2 H.sub.4 OCOCH.sub.3                                                            Br       NHC.sub.2 H.sub.4                                                                          K                              3,5  2,4-Br.sub.2  CH.sub.3                                                                               C.sub.2 H.sub.5                                                                         NHCH.sub.2CH(C.sub.6 H.sub.5)                                                              K                              2    4-SO.sub.2 CH.sub.36-Cl                                                                      "       C.sub.2 H.sub.5                                                                         OC.sub.2 H.sub.4                                                                           K                              2    5-NHCOCH.sub.3                                                                               C.sub.3 H.sub.7                                                                        C.sub.6 H.sub.5                                                                         NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                         K                              2    6-CONHC.sub.6 H.sub.5                                                                        CH.sub.3                                                                               "        NHC.sub.2 H.sub.4                                                                          K                              2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4p-CH.sub.3                                                               OC.sub.2 H.sub.4                                                                           K                              2    4-Cl6-SC.sub.6 H.sub.5                                                                       "       H        OC.sub.2 H.sub.4                                                                           K                              2    4-C.sub.2 H.sub.5                                                                            "       CONHC.sub.2 H.sub.5                                                                     NHC.sub.3 H.sub.6                                                                          K                              2    4-OCH.sub.3   C.sub.2 H.sub.5                                                                        CH.sub.3 OC.sub.2 H.sub.4                                                                           K                              2    4-SCN         C.sub.4 H.sub.6p-OCH.sub.3                                                             C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4                                                                          K                              2    4-Br6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                    C.sub.2 H.sub.5                                                                        SCN      "           K                              2    5-NHCOCH.sub.3                                                                               C.sub.2 H.sub.5                                                                        CONH.sub.2                                                                              "           K                              3    H             CH.sub.3                                                                               CH(CH.sub.3).sub.2                                                                      "           K                              3    2-COCH.sub.3  "       C.sub.6 H.sub.5                                                                         "           K                              3    2-COCH.sub.3  C.sub.6 H.sub.4p-CH.sub.3                                                              C.sub.2 H.sub.5                                                                         NHC.sub.2 H.sub.4 OCH.sub.2                                                                K                              2    4-SCN         C.sub.6 H.sub.5                                                                        H        NHC.sub.2 H.sub.4                                                                          K                              2    4-SO.sub.2 CH.sub.3                                                                          "       "        "           K                              4    2-CONH.sub.2  3-NHCOCH.sub.3                                                                         "        "           K                              4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "       "        "           K                              4    2-SC.sub.6 H.sub. 5                                                                          "       "        "           K                              2    4-Cl          "       "        "           K                              __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________      ##STR17##                                                                     Position                                                                            R.sup.1       R.sup.4  R.sup.11    X'Z         M                          __________________________________________________________________________     2    H             H        CH.sub.3    NHC.sub.2 H.sub.4                                                                          K                          2    H             H        C.sub.6 H.sub.5p-OCH.sub.3                                                                 "           K                          2    H             H        CF.sub.3    "           K                          2    H             H        COOC.sub.2 H.sub.5                                                                         "           K                          2    H             H                                                                                        ##STR18##  "           Na                         2    H             H        C.sub.6 H.sub.5                                                                            "           K                          2    H             C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.4p-Br                                                                        "           K                          2    4-C.sub.6 H.sub.5NN                                                                          "        C(CH.sub.3).sub.3                                                                          "           K                          2    4-Br          "        C.sub.6 H.sub.11                                                                           "           Na                         2    4,6-Br.sub.2  "        C.sub.6 H.sub.5                                                                            "           Na                         2    6-Br          C.sub.6 H.sub.5 SO.sub.2                                                                CH.sub.3    N(CH.sub.3)C.sub.2 H.sub.4                                                                 Na                         2    4-CH.sub.3 SO.sub.26-Br                                                                      C.sub.2 H.sub.5 SO.sub.2                                                                "           NHC.sub.2 H.sub.4                                                                          K                          2    H                                                                                             ##STR19##                                                                              "           N(C.sub.6 H.sub.5)C.sub.2                                                                  K.sub.4                    2,3  H                                                                                             ##STR20##                                                                              CH.sub.3    NHC.sub.2 H.sub.4                                                                          K                          3,5  H             CH.sub.3 CONH.sub.2  NHCH.sub.2CH(C.sub.6 H.sub.5)                                                              K                          3,5  2,4-Br.sub.2  C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.5                                                                            OC.sub.2 H.sub.4                                                                           K                          2    4-SO.sub.2 CH.sub.36-Cl                                                                      C.sub.2 H.sub.4 CN                                                                      "           NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     K                          2    5-NHCOCH.sub.3                                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                             "           NHC.sub.2 H.sub.4                                                                          K                          2    6-CONHC.sub.6 H.sub.5                                                                        C.sub.6 H.sub.11                                                                        CF.sub.3    OC.sub.2 H.sub.4                                                                           K                          2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.4p-Cl                                                                        OC.sub.2 H.sub.4                                                                           K                          2    4-Cl6-SC.sub.6 H.sub.5                                                                       CH.sub.2 C.sub.6 H.sub.5                                                                CONHC.sub.2 H.sub.5                                                                        NHC.sub.3 H.sub.6                                                                          K                          2    4-C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.4 CN                                                                      CH(CH.sub.3).sub.2                                                                         OC.sub.2 H.sub.4                                                                           K                          2    4-OCH.sub.3   C.sub.2 H.sub.5                                                                         "           NHC.sub.2 H.sub.4                                                                          K                          2    4-SCN         C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                                                                            "           K                          2    4-Br6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                    C.sub.2 H.sub.4 CONH.sub.2                                                              CH.sub.3    "           K                          2    5-NHCOCH.sub.3                                                                               C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                                                                            "           K                          3    H             "        C.sub.6 H.sub.5                                                                            "           K                               4-SCN         C.sub.6 H.sub.5                                                                         CH.sub.3    "           K                          2    4-SO.sub.2 CH.sub.3                                                                          "        "           "           K                          4    2-CONH.sub.2  3-NHCOCH.sub.3                                                                          "           "           K                          4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "        "           "           K                          4    2-SC.sub.6 H.sub.5                                                                           "        "           "           K                          2    4-Cl          "        "           "           K                          __________________________________________________________________________

                                      TABLE 7                                      __________________________________________________________________________      ##STR21##                                                                     Position                                                                            R.sup.1  Q  Q' R.sup.12                                                                              R.sup.13                                                                              X'Z     M                                    __________________________________________________________________________     2    H        CO CO C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                       NHC.sub.2 H.sub.4                                                                      Na                                   2    H        CO CO CH.sub.3                                                                              CH.sub.2 OH                                                                           "       Na                                   2    H        CN CO --     NHCO.sub.2 C.sub.2 H.sub.5                                                            OC.sub.2 H.sub.4                                                                       Na                                   2    H        CN CO --     CH.sub.3                                                                              NHC.sub.2 H.sub.4                                                                      Na                                   2    H        CO SO.sub.2                                                                          NH.sub.2                                                                              OC.sub.6 H.sub.5                                                                      "       Na                                   2    H        CO SO.sub.2                                                                          CH.sub.3                                                                              OCH.sub.3                                                                             "       Na                                   2    H        CN SO.sub.2                                                                          --     C.sub.6 H.sub.5                                                                       "       Na                                   2    4-C.sub.6 H.sub.5NN                                                                     CO CO CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2                                                          "       K                                    2    4-Br     CO CO 1,2-C.sub.6 H.sub.4                                                                          "       K                                    2    4,6-Br.sub.2                                                                            CO CO C.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                      "       K                                    2    6-Br     CO CO CF.sub.3                                                                              H      "       K                                    2    4-CH.sub.3 SO.sub.26-Br                                                                 CO CO OCH.sub.3                                                                             H      "       K                                    2    H        CO CO CH.sub.2 Cl                                                                           H      "       K                                    2,3  H        CO CO "      CH.sub.3                                                                              "       K                                    3,5  H        CO CO NHC.sub.2 H.sub.5                                                                     NH.sub.2                                                                              N(CH.sub.3)C.sub.2 H.sub.4                                                             K                                    3,5  2,4-Br.sub.2                                                                            CO CO NHC.sub.2 H.sub.5                                                                     NH.sub.2                                                                              N(C.sub.6 H.sub.5)C.sub.2 H.sub.4                                                      K                                    2    4-SO.sub.2 CH.sub.36-Cl                                                                 CO CO OC.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                       NHC.sub.2 H.sub.4                                                                      K                                    2    5-NHCOCH.sub.3                                                                          CO CO OCH.sub.2C.sub.6 H.sub.5                                                              "      NHC.sub.2 H.sub.4                                                                      K                                    2    6-CONHC.sub.6 H.sub.5                                                                   CO CO OC.sub.6 H.sub.11                                                                     OCH.sub.3                                                                             NHC.sub.2 H.sub.4                                                                      K                                    2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                           CO CO C.sub.6 H.sub.5                                                                       OCH.sub.3                                                                             NHC.sub. 2 H.sub.4                                                                     K                                    2    4-Cl6-SC.sub.6 H.sub.5                                                                  CO CO NHCOC.sub.2 H.sub.5                                                                   NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                      K                                    2    4-C.sub.2 H.sub.5                                                                       CO CO NHSO.sub.2 C.sub.2 H.sub.5                                                            NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                      K                                    2    4-OCH.sub.3                                                                             CO CO NHCOC.sub.6 H.sub.5                                                                   NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                      K                                    2    4-SCN    CO CO OC.sub.2 H.sub.5                                                                      NHCO.sub.2 C.sub.2 H.sub.5                                                            NHC.sub.2 H.sub.4                                                                      K                                    2    4-SCN    CO CO CH.sub.3                                                                              NHC.sub.6 H.sub.5                                                                     "       K                                    2    4-SO.sub.2 CH.sub.3                                                                     CO CO "      "      "       K                                    4    2-CONH.sub.2                                                                            CO CO "      "      "       K                                    4    2-SO.sub.2 C.sub.6 H.sub.5                                                              CO CO "      "      "       K                                    4    2-SC.sub.6 H.sub.5                                                                      CO CO "      "      "       K                                    2    4-Cl     CO CO "      "      "       K                                    __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________      ##STR22##                                                                                        OH                                                          Position                                                                            R.sup.1       Position                                                                            R.sup.2  X'Z         M                                 __________________________________________________________________________     2    H             2    5-CH.sub.3                                                                              NHC.sub.2 H.sub.4                                                                          Na                                2    H             2    5-CH.sub.3                                                                              OC.sub.2 H.sub.4                                                                           Na                                2    H             2    5-OCH.sub.3                                                                             NHC.sub.2 H.sub.4                                                                          K                                 2    H             2    5-Cl     "           Na                                2    H             2    5-Cl     "           Na                                2    H             4    3-OCH.sub.3                                                                             "           K                                 2    H             4    3-OCH.sub.3                                                                             "           K                                 2    4-C.sub.6 H.sub.5NN                                                                          3,4  H        "           Na                                2    4-Br          4    2-NHC.sub.6 H.sub.5                                                                     "           Na                                2    4,6-Br.sub.2  2    5-NHCOCH.sub.3                                                                          "           Na                                2    6-Br          3,4  H        N(CH.sub.3)C.sub.2 H.sub.4                                                                 K                                 2    4-CH.sub.3 SO.sub.2 6-Br                                                                     2                                                                                    ##STR23##                                                                              NHC.sub.2 H.sub.4                                                                          K                                                         C.sub.2 H.sub.4 OSO.sub.3 K                            2    H             2    5-C.sub.6 H.sub.11                                                                      NHC.sub.2 H.sub.4                                                                          K                                 2,3  H             2    5-OC.sub.6 H.sub.5                                                                      N(C.sub.6 H.sub.5)C.sub.2 H.sub.4                                                          K                                 3,5  H             2    5-SCH.sub.3                                                                             NHC.sub.2 H.sub.4                                                                          K                                 3,5  2,4-Br.sub.2  2    5-SC.sub.6 H.sub.5                                                                      NHCH.sub.2CH(C.sub.6 H.sub.5)                                                              Na                                2    4-SO.sub.2 CH.sub.36-Cl                                                                      2    5-NHCOOCH.sub.3                                                                         OC.sub.2 H.sub.4                                                                           Na                                2    5-NHCOCH.sub.3                                                                               2    5-NHSO.sub.2 CH.sub.3                                                                   NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4                                                         Na                                2    6-CONHC.sub.6 H.sub.5                                                                        2    5-NHCOCH.sub.3                                                                          NHC.sub.2 H.sub.4                                                                          NH.sub.4                          2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                2    5-NHCOCH.sub.2 Cl                                                                       OC.sub.2 H.sub.4                                                                           K                                 2    4-Cl6-SC.sub.6 H.sub.5                                                                       2    5-NHCOC.sub.2 H.sub.4 OH                                                                OC.sub.2 H.sub.4                                                                           K                                 2    4-C.sub.2 H.sub.5                                                                            2    5-Cl     NHC.sub.3 H.sub.6                                                                          K                                 2    4-OCH.sub.3   2    5-NHCONHC.sub.2 H.sub.5                                                                 OC.sub.2 H.sub.4                                                                           NH.sub.4                          2    4-SCN         2    5-NHCON(C.sub.2 H.sub.5).sub.2                                                          NHC.sub.2 H.sub.4                                                                          K                                 2    4-Br6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                    2    5-CH.sub.3                                                                              "           K                                 2    5-NHCOCH.sub.3                                                                               2    5-NHCOCH.sub.3                                                                          "           K                                 3    H             4    H        "           Na                                2    4-SCN         2    5-CH.sub.3                                                                              "           Na                                2    4-SO.sub.2 CH.sub.3                                                                          "    "        "           Na                                4    2-CONH.sub.23-NHCOCH.sub.3                                                                   "    "        "           Na                                4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "    "        "           Na                                4    2-SC.sub.6 H.sub.5                                                                           "    "        "           Na                                2    4-Cl          "    "        "           Na                                __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________      ##STR24##                                                                                        OH                                                          Position                                                                            R.sup.1       Position                                                                            R.sup.2   R.sup.14                                                                               X'Z         M                        __________________________________________________________________________     2    H             2    H         6-SO.sub.2 N(CH.sub.3).sub.2                                                           NHC.sub.2 H.sub.4                                                                          Na                       2    H             2    H         "       "           "                        2    H             2    3-CONH.sub.2                                                                             H       "           Na                       2    H             4    H         H       N(CH.sub.3)C.sub.2 H.sub.4                                                                 "                        2    H             4    H         H       OC.sub.2 H.sub.4                                                                           K                        2    H             2,6  H         H       OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                        2    H             2    H         H       OC.sub.2 H.sub.4                                                                           K                        2    4-C.sub.6 H.sub. 5NN                                                                         "    H         6-SO.sub.2 NHCH.sub.3                                                                  OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                        2    4-Br          2    3-CONH.sub.2                                                                             H       NHC.sub.2 H.sub.4                                                                          Na                       2    4,6-Br.sub.2  2    3-CONHC.sub.6 H.sub.5                                                                    H       NHCH(C.sub.2 H.sub.5)CH.sub.2                                                              Na                       2    6-Br          2    3-CONHC.sub.6 H.sub.4p                                                                   H       OC.sub.2 H.sub.4                                                                           NH.sub.4                                         OC.sub.2 H.sub.4 OH                                    2    4-CH.sub.3 SO.sub.26-Br                                                                      4    H         H       NHC.sub.2 H.sub.4                                                                          Na                       2    H             4    H         H       NHC.sub.2 H.sub.4                                                                          Na                       2,3  H             4    H         H       "           "                        3,5  H             2    H         H       NHC.sub.2 H.sub.4                                                                          K                        3,5  2,4-Br.sub.2  2    "         "       NHCH.sub.2CH(C.sub.6 H.sub.5)                                                              K                        2    4-SO.sub.2 CH.sub.36-Cl                                                                      2    3-CO.sub.2 CH.sub.3                                                                      "       OC.sub.2 H.sub.4                                                                           Na                       2    5-NHCOCH.sub.3                                                                               2    "         "       NHC.sub.2 H.sub.4 OC.sub.2                                                     H.sub.4     Na                       2    6-CONHC.sub.6 H.sub.5                                                                        2,4  H         H       NHC.sub.2 H.sub.4                                                                          NH.sub.4                 2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                2    3-COCH.sub.2 Cl                                                                          "       OC.sub.2 H.sub.4                                                                           K                        2    4-Cl 6-SC.sub.6 H.sub.5                                                                      4    H         "       OC.sub.2 H.sub.4                                                                           K                        2    4-C.sub.2 H.sub.5                                                                            4    H         H       NHC.sub.3 H.sub.6                                                                          K                        2    4-OCH.sub.3   4    H         "       OC.sub.2 H.sub.4                                                                           NH.sub.4                 2    4-SCN         4    H         "       NHC.sub.2 H.sub.4                                                                          K                        2    4-Br6-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                    4    H         "       "           "                        2    5-NHCOCH.sub.3                                                                               2    3-CONHC.sub.6 H.sub.5                                                                    "       "           "                        3    H             2    H         "       N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     "                        2    4-SCN         2    3-CONHC.sub.4 H.sub.9n                                                                   "       NHC.sub.2 H.sub.4                                                                          "                        2    4-SO.sub.2 CH.sub.3                                                                          "    "         "       "           "                        4    2-CONH.sub.23-NHCOCH.sub.3                                                                   "    "         "       "           "                        4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "    "         "       "           "                        4    2-SC.sub.6 H.sub.5                                                                           "    "         "       "           "                        2    4-Cl          "    "         "       "           "                        __________________________________________________________________________

                                      TABLE 10                                     __________________________________________________________________________      ##STR25##                                                                     Position                                                                            R.sup.1       R.sup.16      R.sup.17                                                                            R.sup.2                                                                             R.sup.14                                                                            X'Z         M                  __________________________________________________________________________     2    H             C.sub.6 H.sub.11                                                                             H    H    H    NHC.sub.2 H.sub.4                                                                          Na                 2    H             C.sub.2 H.sub.4 CONH.sub.2                                                                   H    H    "    "           "                  2    H             C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                                          H    H    8-OH "           Na                 2    H             C.sub.2 H.sub.4 NHSO.sub.2 CH.sub.3                                                          H    H    H    N(CH.sub.3)C.sub.2                                                             H.sub.4     "                  2    H                                                                                             ##STR26##    H    3-OCH.sub.3                                                                         8-OH OC.sub.2 H.sub.4                                                                           K                  2    H             C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                                   H    H    H    OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                  2    H             CH(CH.sub.3)C.sub.2 H.sub.5                                                                  H    H    H    OC.sub.2 H.sub.4                                                                           K                  2    4-C.sub.6 H.sub.5NN                                                                          CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.3                                                    CH.sub.3                                                                            H    H    OC.sub.2 H.sub.4 OC.sub.2                                                      H.sub.4     K                  2    4-Br          C.sub.6 H.sub.5                                                                              H    3-OCH.sub.3                                                                         H    NHC.sub.2 H.sub.4                                                                          Na                 2    4,6-Br.sub.2  C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.4 OH                                                                  "    H    NHCH(C.sub.2 H.sub.5)CH.su                                                     b.2         Na                 2    6-Br          CH.sub.2 CH(OH)CH.sub.2 OH                                                                   "    H    H    OC.sub.2 H.sub.4                                                                           NH.sub.4           2    4-CH.sub.3 SO.sub.26-Br                                                                      C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                            H    H    H    NHC.sub.2 H.sub.4                                                                          Na                 2    H             (CH.sub.2).sub.3 NHCOCH.sub.3                                                                H    H    H    NHC.sub.2 H.sub.4                                                                          Na                 2,3  H             C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                                                          H    H    H    "           "                  3,5  H             C.sub.3 H.sub.6 OCH.sub.3                                                                    H    H    H    NHC.sub.2 H.sub.4                                                                          K                  3,5  2,4-Br.sub.2  CH.sub.2 C.sub.6 H.sub.5                                                                     CH.sub.2 C.sub.6 H.sub.5                                                            "    "    NHCH.sub.2CH(C.sub.6                                                           H.sub.5)    K                  2    4-SO.sub.2 CH.sub.36-Cl                                                                      C.sub.6 H.sub.11                                                                             H    H    "    OC.sub.2 H.sub.4                                                                           Na                 2    5-NHCOCH.sub.3                                                                               C.sub.2 H.sub.4 CONH.sub.2                                                                   H    "    "    NHC.sub.2 H.sub.4                                                              OC.sub.2 H.sub.4                                                                           Na                 2    6-CONHC.sub.6 H.sub.5                                                                        C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                                          H    H    8-OCH.sub.3                                                                         NHC.sub.2 H.sub.4                                                                          NH.sub.4           2    4,6-(SO.sub.2 CH.sub.3).sub.2                                                                 ##STR27##    H    3-OC.sub.2 H.sub.5                                                                  8-OC.sub.2 H.sub.5                                                                  OC.sub.2 H.sub.4                                                                           K                  2    4-Cl6-SC.sub.6 H.sub.5                                                                        ##STR28##    H    H    H    OC.sub.2 H.sub.4                                                                           K                  2    4-C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                                   H    H    H    NHC.sub.3 H.sub.6                                                                          K                  2    4-OCH.sub.3   CH(CH.sub.3)C.sub.2 H.sub.5                                                                  H    H    "    OC.sub.2 H.sub.4                                                                           NH.sub.4           2    4-SCN         CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.3                                                    H    H    "    NHC.sub.2 H.sub.4                                                                          K                  2    4-Br6-SO.sub. 2 C.sub.6 H.sub.4p-OCH.sub.3                                                   C.sub.6 H.sub.5                                                                              H    3-C.sub.2 H.sub.5                                                                   "    "           "                  2    5-NHCOCH.sub.3                                                                               C.sub.2 H.sub.5                                                                              "    H    "    "           "                  3    H             CH.sub.2 CH(OH)CH.sub.2 OH                                                                   "    H    "    N(C.sub.6 H.sub.5)C.sub.2                                                      H.sub.4     "                  2    4-SCN         CH.sub.2 CH.sub.3                                                                            "    "    "    NHC.sub.2 H.sub.4                                                                          "                  2    4-SO.sub.2 CH.sub.3                                                                          "             "    "    "    NHC.sub.2 H.sub.4                                                                          "                  4    2-CONH.sub.2  3-NHCOCH.sub.3                                                                               "    "    "    "           "                  4    2-SO.sub.2 C.sub.6 H.sub.5                                                                   "             "    "    "    "           "                  4    2-SC.sub.6 H.sub.5                                                                           "             "    "    "    "           "                  2    4-Cl          "             "    "    "    "           "                  __________________________________________________________________________

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A dye of the formula: ##STR29## wherein the phenyl ring containing the ##STR30## group or groups, is unsubstituted or substituted with 1-3 R¹ substituents independently selected from alkyl, alkoxy, thiocyano, alkylthio, arylazo, arylthio, aroyl, carbamoyl, alkylcarbamoyl, alkanoyl, alkylsulfonyl, arylsulfonyl, sulfamoyl, SO₂ NH(alkyl), SO₂ N(dialkyl), alkylsulfonamido, alkanoylamino, halogen, trifluoromethyl, and SO₃ (aryl); n is 1 or 2; C is a coupler selected from ##STR31## wherein R² and R¹⁴ each represents up to three groups selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R³ in which X is --CO--, --COO--, or --SO₂ -- andR³ is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R³ also is selected from hydrogen, amino, alkylamino, dialkylamino, arylamino, aryl, and furyl; R⁴ and R⁵ are each selected from hydrogen, alkyl, aryl, cycloalkyl, and alkyl substituted with halogen, CN, OH, alkoxy, aryloxy, alkoxyalkoxy, alkanoyl, alkanoyloxy, carbamoyl, alkylcarbamoyl, sulfamoyl, alkylsulfamoyl, alkoxyalkanoyloxy, and cycloalkyl, and R⁴ and R⁵ together represent a single, combined group --CH₂ CH₂ CH₂ CH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, --CH₂ CH₂ --S--CH₂ CH₂ --, or --CH₂ CH₂ --SO₂ -CH₂ CH₂ --; R⁸ represents one or two groups each selected from hydrogen, alkyl and alkyl substituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, cyclohexoxy, --OH, --Cl and Br; R⁹, R¹⁰ and R¹¹ are each selected from hydrogen, alkyl, phenyl, or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkylthio, benzylthio, cyclohexylthio and phenylthio; Q and Q' are each selected from --CO--, --SO₂ --, or --CN; R¹² and R¹³ are each selected from alkyl, hydroxyalkyl, alkoxy, alkoxycarbonylamino, trifluoromethyl, phenyl or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl, or alkoxy, alkoxycarbonylalkyl, cyanoalkyl, amino, haloalkyl, alkylamino, alkylthio, benzylthio, cyclohexylthio and phenylthio; and R¹² and R¹³ together comprise --CH₂ C(CH₃)₂ CH₂ --, or 1,2--C₆ H₄ -- connecting Q and Q'; R¹⁶ and R¹⁷ are selected from hydrogen, cycloalkyl, aryl, alkyl, and alkyl substituted with alkoxy, hydroxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, sulfamoyl, alkanoylamino, or alkenylsulfonyl, and aryl substituted with hydroxyalkyl; e is 1 or 2; t and t' are each 1 or zero; X' is O, NH, N(alkyl)-, or N(aryl)-; Z is selected from straight- or branched-chain alkylene, and such alkylene substituted with phenyl, halogen, OSO₃ M, alkoxy or aryloxy groups, --CH₂ (CH₂)_(m) V--CH₂ (CH₂)_(P) --, where m is 1, 2 or 3, p is 0, 1, 2 or 3, and V is O, S, SO₂, --SO₂ NH--, --SO₂ N(alkyl)-, --SO₂ N(aryl), --N(SO₂ aryl)-, --NH, --NHCO--, --NHCONH, --N(SO₂ alkyl), or --CON(alkyl); M is H, Na, K or NH₄ ; n is 1 or 2; and wherein each of the above alkyl and alkoxy groups contain from 0 to three of the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; ##STR32## wherein Y is --NH--, --NH-alkyl-, --O--, --S--, or --CH₂ O--; --S--R⁶, wherein R⁶ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or ##STR33## --SO₂ R³ ; --COOR³ ; --OXR³ ; --NH--X--R³ ; --X--R³ ; --SO₂ NR⁷ R⁷ ; wherein R³ and X are as defined above and each R⁷ is selected from H and R³ ; alkoxy, alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; or phenoxy substituted with one or more of alkyl, alkoxy or halogen.
 2. The dye according to claim 1 of the formula ##STR34##
 3. The dye according to claim 1 of the formula ##STR35##
 4. The dye according to claim 1 of the formula ##STR36##
 5. The dye according to claim 1 of the formula ##STR37## 